WO2013161377A1

WO2013161377A1 - Naphthobisthiadiazole derivative

Info

Publication number: WO2013161377A1
Application number: PCT/JP2013/055129
Authority: WO
Inventors: 和男瀧宮; 格尾坂; 和彰川島
Original assignee: 国立大学法人広島大学; 三協化成株式会社
Priority date: 2012-04-26
Filing date: 2013-02-27
Publication date: 2013-10-31
Also published as: KR20140137442A; CA2871722A1; US9209409B2; EP2842958A4; IN2014DN09769A; EP2842958A1; US20150112081A1; JP2013227260A; JP6057364B2; CN104254538A

Abstract

A naphthobisthiadiazole derivative is represented by formula 1. In formula 1, Z is hydrogen, a boronic acid group, a boronic acid ester group, a trifluoroborate salt group, or a triolborate salt group, and at least one is a boronic acid group, boronic acid ester group, trifluoroborate salt group, or triolborate salt group. The naphthobisthiadiazole derivative is an organic boron compound that can be converted to a multipurpose compound by a Suzuki-Miyaura coupling method or the like, and that can be used as a precursor for complex compounds. Consequently, on the basis of the naphthobisthiadiazole derivative, research, development and practical use of low-molecular-weight compounds and high-molecular-weight compounds that are useful as a variety of organic semiconductor materials, and the like, becomes possible.

Description

Naphthobisthiadiazole derivatives

The present invention relates to a naphthobisthiadiazole derivative.

Research, development, and practical application of various organic semiconductor materials are being promoted, and organic semiconductor materials having a naphthobisthiadiazole skeleton are considered promising. Non-Patent Document 1 discloses a polymer compound having a naphthobisthiadiazole skeleton and a synthesis method thereof.

In Non-Patent Document 1, naphthobisthiadiazole is brominated, and this bromide and a heteroaromatic ring such as a thiophene ring having an organic metal such as organotin or an aromatic ring are bonded using a transition metal catalyst, and used as an organic semiconductor material. We have available high molecular compounds. However, with this method, organic metals may not be introduced depending on the heteroaromatic ring or aromatic ring to be bonded, and organic tin and the like are toxic and difficult to industrially use. There is a problem that it is scarce.

The present invention has been made in view of the above matters, and an object of the present invention is to provide a naphthobisthiadiazole derivative that can be developed into various organic semiconductor materials having a naphthobisthiadiazole skeleton and is excellent in versatility. It is in.

The naphthobisthiadiazole derivative according to the present invention is
Represented by Equation 1,

(In Formula 1, Z represents hydrogen, a boronic acid group, a boronic acid ester group, a trifluoroborate base or a triol borate base, and at least one is a boronic acid group, a boronic acid ester group, a trifluoroborate base or a triol borate base. is there.)
It is characterized by that.

The Z is preferably represented by any one of Formulas 11 to 19.

(In formula 12, R represents an alkyl group.)

The naphthobisthiadiazole derivative according to the present invention has a boronic acid group, a boronic acid ester group, a trifluoroborate base or a triol borate base. Boronic acid groups, boronic acid ester groups, trifluoroborate bases or triol borate bases can be converted into various compounds by coupling reactions such as Suzuki-Miyaura coupling, and can be used as precursors for complex compounds. Excellent in properties. Therefore, based on the naphthobisthiadiazole derivative, it becomes possible to research, develop and put into practical use low molecular compounds and high molecular compounds having a naphthobisthiadiazole skeleton useful for various organic semiconductor materials.

(Naphthobisthiadiazole derivatives)
The naphthobisthiadiazole derivative according to the present embodiment is represented by Formula 1.

In the above formula 1, Z is hydrogen, boronic acid group, boronic ester group, trifluoroborate base or triol borate base, and at least one is boronic acid group, boronic ester group, trifluoroborate base or triol borate base is there. The boronic acid group, boronic ester group, trifluoroborate base or triol borate base is not particularly limited, but examples thereof include functional groups represented by Formulas 11 to 19. In formula 12, R represents an alkyl group.

The naphthobisthiadiazole derivative is an organoboron compound, which can be converted into various compounds by a coupling reaction such as Suzuki-Miyaura coupling, and can be used as a precursor of a complex compound.

For this reason, a naphthobisthiadiazole derivative is reacted with a halide having a π-conjugated electronic structure such as a donor functional group, an acceptor functional group, or a thiophene ring, and a low molecular compound or a high molecular compound having a naphthobisthiadiazole skeleton. Etc. can be easily synthesized.

Therefore, research, development and practical application of low-molecular compounds and high-molecular compounds having a naphtho-bisthiadiazole skeleton useful for various organic semiconductor materials and the like based on naphtho-bisthiadiazole derivatives can be achieved. Naphthobisthiadiazole derivatives are relatively stable against water, air, and the like, and are excellent in operability.

(Method for synthesizing naphthobisthiadiazole derivatives)
There is no restriction | limiting in particular in the synthesis | combining method of the naphthobisthiadiazole derivative which concerns on this Embodiment mentioned above, It can synthesize | combine combining a well-known synthesis method. As an example, it can be synthesized as follows.

Naphthobisthiadiazole (naphtho [1,2-c: 5,6-c ′] bis [1,2,5] thiadiazole) is reacted with a diboronic acid ester. The bond between carbon and hydrogen located at the 4th and 9th positions of naphthobisthiadiazole is cleaved, and a boronic acid ester group is bonded at the same position to obtain a naphthobisthiadiazole derivative represented by Formula 1.

The diboronic acid ester used is not particularly limited, and examples thereof include diboronic acid esters such as bis (pinacolato) diboron, bis (neopentylglycolato) diboron, bis (hexyleneglycolato) diboron, and bis (catecholato) diboron.

In addition, it is preferable to react by adding a CH activation catalyst. The bond between carbon and hydrogen at the 4th and 9th positions of naphthobisthiadiazole is likely to be broken. Thereby, the bond between the carbon from which hydrogen has been eliminated and the boronic ester group is promoted. The CH activation catalyst is not limited as long as it can break a carbon-hydrogen bond, and examples thereof include transition metals such as palladium, iridium, ruthenium, and catalysts containing these. In addition, when using the catalyst containing iridium or iridium as a CH activation catalyst, it is good to add the compound used as a ligand.

A naphthobisthiadiazole derivative having a boronic acid can be obtained by deesterification of the naphthobisthiadiazole derivative having a boronic acid ester.

Further, naphthobisthiadiazole derivatives having trifluoroborate base or triolborate base can be obtained by using boronic acid or naphthobisthiadiazole derivatives having boronate ester, for example Potassium Organotrifluoroborates: New Perspectives in Organic Synthesis; Sylvain Darses and Jean-Pierre Genet , Chem. Rev., 108, 288-325 (2008) and Cyclic Triolborates: Air- and Water-Stable Ate Complexes of Organoboronic Acids; sunYasunori Yamamoto, Miho Takizawa, Xiao-Qiang Yu, Norioiengewand , 928-931 (2007).

Also, a boronic ester group is obtained by reacting dibromonaphthothiadiazole (4,9-dibromonaphtho [1,2-c: 5,6-c ′] bis [1,2,5] thiadiazole) with a diboronic ester. It is also possible to synthesize naphthobisthiadiazole derivatives having

Naphthobisthiadiazole (naphtho [1,2-c: 5,6-c ′] bis [1,2,5] thiadiazole) and dibromonaphthothiadiazole (4,9-dibromonaphtho [1,2-c: 5 , 6-c ′] bis [1,2,5] thiadiazole) is a combination of Sulfur Nitride in Organic Chemistry. Part 19. Selective Formation of Benzo- and Benzobis [1,2,5] thiadiazole Skeleton in the Reaction of Tetrasulfur Tetranitride with Naphthalenols and Related Compounds; Shuntaro MATAKA, Kazufumi TAKAHASHI, Youji IKEZAKI, Taizo Hatta, Akiyoshi TORII, and Masashi TASHIRO;

Hereinafter, the naphthobisthiadiazole derivative and the synthesis method thereof will be described in detail based on examples, but the present invention is not limited thereto.

(Naphtho [1,2-c: 5,6-c ′] bis [1,2,5] thiadiazole-4,9-bis (boronic acid pinacol ester) (hereinafter, synthesis of compound 1)
Under a nitrogen atmosphere, 20 mL of cyclohexane as a solvent in a three-necked flask, bis (1,5-cyclooctadiene) di-μ-methoxydiiridium (I) (33 mg, 0.05 mmol) as a CH activation catalyst, 4,4′-Di-tert-butyl-2,2′-dipyridyl compound (27 mg, 0.1 mmol) was added as a ligand, and the mixture was stirred under reflux for about 1 hour under light shielding.
Next, bis (pinacolato) diboron (283 mg, 1.1 mmol) was added, and the mixture was further refluxed for 30 minutes.
Thereafter, naphtho [1,2-c: 5,6-c ′] bis [1,2,5] thiadiazole (122 mg, 0.5 mmol) was added and refluxed for 12 hours.
After cooling to room temperature, cyclohexane was removed, and the crude product was recrystallized using chloroform to obtain Compound 1 (174 mg, 70%) as milky white needle crystals.

The above reaction formula is shown below.

Moreover, the measurement result of the obtained compound 1 is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , ppm) δ 1.50 (s, 24H, CH ₃ ), 9.52 (s, 2H, ArH)

(Synthesis of 4,9-bis (thiophen-2-yl) -naphtho [1,2-c: 5,6-c ′] bis [1,2,5] thiadiazole (hereinafter Compound 2))
Under a nitrogen atmosphere, Compound 1 (99.2 mg, 0.2 mmol), 2-bromothiophene (72.7 mg, 0.44 mmol), Pd (PPh ₃ ) ₄ (4.8 mg, 0.004 mmol), potassium carbonate (1 .11 g, 8 mmol), distilled water (4 ml) and toluene (10 ml) were added to a three-necked flask and stirred at reflux for 12 hours.
The reaction solution was allowed to cool to room temperature, poured into water, and the precipitated solid was collected by filtration. The obtained solid was recrystallized from chloroform to obtain Compound 2 (67 mg, 82%) as a red solid.

The above reaction formula is shown below.

Moreover, the measurement result of the obtained compound 2 is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , ppm) δ 7.29 (d, 2H, ArH), 7.55 (d, 2H, ArH), 8.33 (d, 2H, ArH), 8.99 (s, 2H)

(Synthesis of 4,9-dibromonaphtho [1,2-c: 5,6-c ′] bis [1,2,5] thiadiazole (hereinafter, compound 3))
Compound 1 (49.6 mg, 0.1 mmol), copper (II) bromide (134 mg, 0.6 mmol), methanol (4 mL), distilled water (2 mL) and NMP (12 mL) were added to the reaction vessel and refluxed. After cooling, the precipitated solid was collected by filtration and washed with hydrochloric acid, water, and methanol to obtain Compound 3 (3 mg, 70%).

The above reaction formula is shown below.

Moreover, the measurement result of the obtained compound 3 is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , ppm) δ 9.14 (s, 2H, ArH)

(Poly {naphtho [1,2-c: 5,6-c ′] bis [1,2,5] thiadiazole-4,9-diyl-alt- (3′4 ″ -di (2-decyltetradecyl ) -2,2 ′; 5 ′, 2 ″; 5 ″, 2 ′ ″-quarterthiophene-5,5 ′ ″-diyl)} (Synthesis of Compound 4))
Compound 1 (24.8 mg, 0.05 mmol), Compound A (58.1 mg, 0.05 mmol), Pd (PPh ₃ ) ₂ Cl ₂ (1.7 mg, 0.0025 mmol), 2M K ₂ under nitrogen atmosphere. An aqueous CO ₃ solution (1.6 ml), toluene (2.4 ml) and a drop of Aliquat 336 were sealed in a reaction vial.
This was set in a microwave synthesizer and reacted at 180 ° C. for 2 hours. Thereafter, the reaction solution was poured into a large excess of methanol and stirred.
The precipitate was collected by filtration using a Soxhlet extraction filter, and components soluble in these solvents were removed by Soxhlet extraction using methanol and chloroform.
Furthermore, the filter residue was subjected to Soxhlet extraction using chlorobenzene, and the resulting solution was poured into a large excess of methanol.
The precipitate was collected by filtration to obtain Compound 4 (27 mg, 43%) as a dark green solid.

The above reaction formula is shown below.

Moreover, the measurement result of the obtained compound 4 is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , ppm) δ around 9.0 (br, 2H, ArH), around δ7-8 (br, 6H, ArH), around δ2.5 (br, 4H), δ0.8 ~ Near 2 (br, 94H)

It should be noted that the present invention can be variously modified and modified without departing from the scope of the present invention. Further, the above-described embodiment is for explaining the present invention, and does not limit the scope of the present invention.

This application is based on Japanese Patent Application No. 2012-101625 filed on April 26, 2012. In this specification, the entire specification and claims of Japanese Patent Application No. 2012-101625 are incorporated by reference.

As described above, naphthobisthiadiazole derivatives can be converted into various compounds by coupling reactions such as Suzuki-Miyaura coupling, and can be used as precursors for complex compounds and have excellent versatility. Therefore, research, development and practical application of low-molecular compounds and high-molecular compounds having a naphtho-bisthiadiazole skeleton useful for various organic semiconductor materials and the like based on naphtho-bisthiadiazole derivatives are expected.

Claims

Represented by Equation 1,
A naphthobisthiadiazole derivative characterized by that.

(In Formula 1, Z represents hydrogen, a boronic acid group, a boronic acid ester group, a trifluoroborate base or a triol borate base, and at least one is a boronic acid group, a boronic acid ester group, a trifluoroborate base or a triol borate base. is there.)
Z is represented by any one of formulas 11 to 19,

(In formula 12, R represents an alkyl group.)
The naphthobisthiadiazole derivative according to claim 1, wherein